| Project/Area Number |
11650808
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
触媒・化学プロセス
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| Research Institution | Kobe University |
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Principal Investigator |
NISHIYAMA Satoru Kobe University Faculty of Engineering, Associate Professor, 工学部, 助教授 (00156126)
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| Co-Investigator(Kenkyū-buntansha) |
TSURUYA Shigeru Kobe University Faculty of Engineering, Professor, 工学部, 教授 (00031120)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1999: ¥2,900,000 (Direct Cost: ¥2,900,000)
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| Keywords | Tin oxide / Zirconium oxide / MCM-41 / Active carbon / Crotonaldehyde / Acetophenone / Hydrogen transfer / Selective reduction / メソポーラス多孔質体 / シリカゲル / 不飽和カルボニル化合物 / 不飽和アルコール / 選択的還元反応 |
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| Research Abstract |
Mesoporous silicate, MCM-41 was synthesized by using hexadecyl trimethyl ammonium bromide as a template. MCM-41, SiO_2, Al_2O_3, TiO_2 and some zeolites were impregnated with some kinds of tin and zirconium salts. The catalyst were calcined and reduced at prescribed temperatures.
The selective reductions of crotonaldehyde and acctophenone were carried out with a secondary alcohol in stainless steel autoclave (30 ml).
Hydrogenation of crotonaldehyde over metallic catalysts produces significant amount of butyraldehyde and 1-butanol, corresponding hydrogenates of C=C doublc bond. The addition of Sn was effective to improve the selectivity of crotyl alcohol, corresponding hydrogenate of carbonyl group over metallic catalysts. The supported Sn and Zr catalysts indicated that carbonyl groups were selectivcly reduced via hydrogen transfer reaction from secondary alcohol added as a solvent (MPV reduction). The effects of support and starting salts were investigated. Silica including MCM-41 was suitable for the support of Sn and Zr. Acidic or basic support was not effective. Zirconium supported on active carbon was also highly active. Neutral porous materials should be selected for the supports. Tin acetate for Sn catalysts and zirconium oxychloride for Zr catalysts were ones of the best starting salts, respectively Dependence of reduction temperature on the yicld of unsaturated alcohol indicated that Sn (II) and Zr (IV) were active species for the selective reduction of carbonyl compounds. Enatiomeric-excess of S-1-phenyl ethanol was improved by the addition of cinconidine in the reation mixture.
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